CN101384515A - Method of producing particles by physical vapor deposition in an ionic liquid - Google Patents

Method of producing particles by physical vapor deposition in an ionic liquid Download PDF

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Publication number
CN101384515A
CN101384515A CNA2007800052004A CN200780005200A CN101384515A CN 101384515 A CN101384515 A CN 101384515A CN A2007800052004 A CNA2007800052004 A CN A2007800052004A CN 200780005200 A CN200780005200 A CN 200780005200A CN 101384515 A CN101384515 A CN 101384515A
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ionic liquid
particle
sediment chamber
liquid
deposition
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CN101384515B (en
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J·J·芬利
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PPG Industries Ohio Inc
PPG Industries Inc
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PPG Industries Inc
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    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
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    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/056—Submicron particles having a size above 100 nm up to 300 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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    • B82—NANOTECHNOLOGY
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    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/06—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
    • C03C17/09—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals by deposition from the vapour phase
    • C—CHEMISTRY; METALLURGY
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    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
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    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
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    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3657—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having optical properties
    • C03C17/366—Low-emissivity or solar control coatings
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/28—Vacuum evaporation by wave energy or particle radiation
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/48—Ion implantation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/02631—Physical deposition at reduced pressure, e.g. MBE, sputtering, evaporation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
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    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/67155—Apparatus for manufacturing or treating in a plurality of work-stations
    • H01L21/67207—Apparatus for manufacturing or treating in a plurality of work-stations comprising a chamber adapted to a particular process
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    • C03C2217/00—Coatings on glass
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    • C03C2217/21—Oxides
    • C03C2217/219—CrOx, MoOx, WOx
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    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
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    • C03C2217/253—Cu
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    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
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    • C03C2217/254—Noble metals
    • C03C2217/256—Ag
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    • C03C2217/00—Coatings on glass
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    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/15—Deposition methods from the vapour phase
    • C03C2218/154—Deposition methods from the vapour phase by sputtering
    • C03C2218/156—Deposition methods from the vapour phase by sputtering by magnetron sputtering
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    • C03C2218/00—Methods for coating glass
    • C03C2218/30—Aspects of methods for coating glass not covered above
    • C03C2218/34—Masking
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal

Abstract

A method is provided for producing particles, such as nanoparticles. The method includes introducing an ionic liquid into a deposition chamber, and directing one or more material toward or depositing one or more materials onto the ionic liquid by physical vapor deposition to form nanoparticles in the ionic liquid.

Description

In ionic liquid, prepare the particulate method by physical vapor deposition
The cross reference of relevant application
The application requires by reference this provisional application to be quoted fully at this in the right of priority of the U.S. Provisional Application 60/759,457 of submission on January 17th, 2006.
Invention field
The present invention relates generally to particle and forms, and in a special non-limiting embodiments, relates to form nano particle in ionic liquid.
Background technology
Nano particle is that dimensional measurement is the microscopic particles of nanometer (nm).The nano particle that makes by semiconductor material, if they enough little (typically less than 10nm), also can be described as quantum dot, the electronic level quantization can take place.
Nano particle has great scientific interest, because they can be effectively as the bridge between massive material and atom or molecular structure.Massive material should have the constant physicals, and is irrelevant with size, but at nanoscale, is not often like this.Can be observed the performance that depends on size, for example the quantum limit in semiconductor grain, the surface plasma resonance in some metal particles and the superparamagnetism in magneticsubstance.Because the multiple potential application in biomedicine, optics and electronic applications, nano particle research is the hot spot region of scientific research at present.
At present, use solution chemical processes to form nano particle usually.For example, can in the presence of reductive agent, the reduction by tetra chlorauric acid prepare gold nano grain.This makes gold ion be reduced to unionized gold atom, deposits with the form of inferior nano particle.In order to stop particle agglomeration, interpolation can stick to the stablizer on the nano grain surface usually.Can use various organic ligands that nano particle is carried out functionalization to obtain to have the hybrid inorganic-organic materials of advanced function.
When being fit to form nano particle, these present solution chemical processes have some shortcomings really.For example, may need heating for multiple times and reactions steps during the course.In addition, some reactants that need may be harmful to the workman, thereby be difficult to operate or have danger when operating.In addition, when final formation nano particle,, make particle agglomeration and be not to keep the individual particle form usually with their classification and packing.
Therefore, it is favourable providing the method for making nano particle and reducing or eliminating the problem that at least some present methods have.
Summary of the invention
Preparation particulate method is provided.Method comprises to be introduced ionic liquid in the sediment chamber, guides one or more materials so that particle to be provided in ionic liquid by physical vapor deposition to ionic liquid.
The method for preparing nano particle comprises to be introduced ionic liquid in the sediment chamber; Find time the sediment chamber to form the vacuum of 1-7 micron Hg; One or more negative electrodes of sputter are to introduce one or more materials to ionic liquid so that form nano particle in ionic liquid in the sediment chamber.
Inventive composition comprises ionic liquid and the nano particle that forms by physical vapor deposition in ionic liquid.
Accompanying drawing is briefly described
Describe the present invention with reference to following accompanying drawing, wherein identical referential data is represented identical parts in entire description.
Fig. 1 is according to the figure of the Cu nano particle specific absorption of inventing formation with respect to wavelength;
Fig. 2 and 3 is FESEM (field-emission scanning electron microscope) of Cu nano particle;
Fig. 4 is the EDX (energy dispersion X ray) of Cu nano particle;
Fig. 5 and 6 is FESEM of Ag nano particle;
Fig. 7 is the XPS (x-ray photoelectron spectroscopy) of Ag nano particle;
Fig. 8 is the figure of the absorbancy of Ag nano particle with respect to wavelength;
Fig. 9 is that tungsten oxide nanometer particulate bound energy is with respect to counting (counts) figure (XPS);
Figure 10 and 11 is tungsten oxide nanometer particulate FESEM;
Figure 12 is the EDX that comprises the nano particle of Tungsten oxide 99.999;
Figure 13 is the figure of the transmissivity of Ag-dielectric lamination on the different substrate with respect to wavelength;
Figure 14 is the FESEM of Ir nano particle;
Figure 15 is the EDX of Ir nano particle; And
Figure 16 is the figure of the absorbancy of Ag nano particle in different ionic liquid with respect to wavelength.
Detailed description of the invention
Space as used herein or direction term, for example " left side ", " right side ", " interior ", " outward ", " on ", D score etc., the present invention as shown in drawings like that touches upon. Yet, should understand energy of the present invention Suppose multiple interchangeable direction, therefore, this term is not thought and is limited. In addition, as All expression sizes, physical properties of in specification and claim, using as used herein,, The numeral of technological parameter, group component, reaction condition etc. is interpreted as in all cases by term " about " Modified. Therefore, unless opposite explanation is mentioned in specification and the claim below Numerical value can be depending on the desired properties that will obtain by the present invention to be changed. At least, do not taste Examination restriction doctrine of equivalents is applied to the scope of claim, each numerical value should be at least according to report Significant digit, and make an explanation by using conventional approximation technique. In addition, disclosed herein All scopes are interpreted as and comprise beginning and end range value and anyly be included in wherein son with all Scope. For example, " 1-10 " scope should be thought and is included in minimum of a value 1 and 10 of maximums and comprises Their any subrange; That is, all subranges be equal to or greater than 1 minimum of a value and begin and with Be equal to or less than 10 maximum end, for example, 1-3.3,4.7-7.5,5.5-10 etc. In addition, As used herein, term " on form ", " on deposition " or " on provide " Refer to from the teeth outwards and form, deposit, provide but unessential and Surface Contact. For example, at substrate The coating of upper formation is not got rid of and is had between the coating of formation and the substrate that one or more layers is identical or not With other coating or the film that form. As used herein, term " polymer " " or " polymerization " Comprise oligomer, homopolymers, copolymer and three copolymers, for example by two or more monomers or poly-The polymer that compound forms. In addition, think all documents, for example but be not restricted to the patent of publication With patent application etc. and in the network address of these all references, by with reference to quoting fully.
In a nonrestrictive embodiment, the invention provides the use physical gas-phase deposite method At room temperature the preparation particle is for example but be not restricted to the side of nano particle in ionic liquid (IL) Method. In a nonrestrictive embodiment, ionic liquid is introduced conventional physical vapour deposition (PVD) dress Put in the settling chamber of conventional sputter deposition apparatus for example or conventional electrical beam evaporation device. Find time to deposit One or more negative electrodes one or more materials of sputtering sedimentation on ionic liquid are used in the chamber. Can make With any conventional negative electrode. The negative electrode that is fit to comprises but is not restricted to the negative electrode that contains metal, contains half The negative electrode of metal and carbon cathode just list and give some instances.
The salt that ionic liquid is is liquid being less than or equal to 400 ℃ of temperature. Be suitable for of the invention process Nonrestrictive ionic liquid comprises the combination of cation and anion. Cation can comprise list, two, Pyridine, the pyrrolidines of replacement, Si Wan Ji Phosphonium, four alkane with trisubstituted imidazoles, replacement Base ammonium, guanidine (guanidiniums), isourea (isouroniums), thiocarbamide (thiouroniums). Anion can comprise chlorion, bromide ion, iodide ion, tetrafluoroborate, Hexafluoro-phosphate radical, two (trimethyl fluoride sulfonyl) imines root, three (pentafluoroethyl group) trifluoro phosphate radical (FAPs), TFMS root, trifluoracetic acid root, methylsulfate, octyl group sulfate radical, sulphur cyanogen Acid group, organic boron acid group, and p-methyl benzenesulfonic acid root. Concrete ionic liquid limiting examples bag Draw together 1-butyl-3-methylimidazole hexafluorophosphate ([BMIM] PF6), 1-hexyl-3-methyl imidazolium tetrafluoroborate ([HMIM] BF4), 1-butyl-3-methyl imidazolium tetrafluoroborate ([BMIM] BF4), two fluoroform sulfimide salt ([the EMIM] (CF of 1-ethyl-3-methylimidazole3SO 2) 2N). Other non-limiting from Sub-liquid can obtain from the Solvent Innovation GmhH of German Cologne, Http:// www.solvent-innovation.com/index_overview.htm. lists. Other Ionic liquid can obtain from the Merk KGaA of German Darmstadt. The change of cation and anion Change and to produce the millions of kinds of ionic liquids that can be suitable for well concrete application.
Ionic liquid also is energy reaction, recirculation and polymeric solvent.Therefore, they have extensive use in industry, for example catalysis, synthetic, electrochemistry, medical science, transmitter, lubricant and separation.In addition, ionic liquid has insignificant vapour pressure and has high thermal stability.With regard to VOC (volatile organic compounds), with conventional organic solvent, for example alcohol, toluene, methylene dichloride (only giving some instances) are compared, and these performances make them become eco-friendly solvent.
Find that in the present invention when the steam that produces by physical vapor deposition (PVD) deposits on ionic liquid in the system in a vacuum, generate nano particle, ionic liquid is as the stable storage of particulate.Use the method for magnetron sputtering below among the embodiment as deposition vapor.Yet, can use the physical deposition method of carrying out in any system in a vacuum to prepare particle.The advantage that the present invention is better than prior art is to contain liquid in vacuum system, and wherein liquid has negligible influence to the pressure of system.Can obtain vacuum coat process required low base pressure and deposition pressure, not have liquid in the Buddhist system that walks back and forth.Ion liquid another advantage is that it is to help chemically treated general solvent (referring to AIChE Journal, (November calendar year 2001) Vol.47,2384-2389 page or leaf, IL ' sin Chemical Processing).Nano particle of the present invention is introduced in the ionic liquid, transfers in the medium with the step of further processing and/or eliminates the multistep chemical treatment step thereby eliminated.In addition, show, the deposited particles volume is directly proportional with deposition pressure, and therefore lower deposition pressure not only is suitable for carrying out free of contamination stabilization process ideally, and is suitable for continuing, reliably preparing for example interior particle of nanoparticle size range of required particle size range.As used herein, " particle " or " nanoparticle size range " refers to the particle that overall dimension is not more than 500nm, for example be not more than 200nm, for example be not more than 100nm or be not more than 50nm, or be not more than 10nm, for example in the scope of 0.1-200nm, for example in the scope of 0.5-200nm, for example in the scope of 1-200nm.Under the pressure that is not more than 50 microns Hg, carry out deposition process, for example be not more than 20 microns Hg, for example be not more than 10 microns Hg, for example be not more than 7 microns Hg, or be not more than 5 microns Hg, and for example be not more than 4 microns Hg, for example be not more than 3 microns Hg, or be not more than 2 microns Hg, for example be not more than 1 micron Hg.As is understood, 1 micron equals 0.001 torr.In addition, ionic liquid can stop particle agglomeration without any need for the additive that will increase vapour pressure and limit present method operational capability under low pressure.Can use the additive that increases viscosity but do not influence vapour pressure.The ionic liquid that can mix different viscosity is to adjust the viscosity of final liquid.
Following non-restrictive example has illustrated all respects of the present invention.In these embodiments, in vacuum system on ionic liquid sputtering sedimentation copper, silver and Tungsten oxide 99.999.After introducing liquid, 10 -6-10 -7The vacuum system base pressure of torr scope is not compared with conventional solid substrate and is significantly differently changed, because ion liquid vapour pressure can be ignored.Also can under 7 microns Hg or littler pressure, deposit.Pressure does not change in deposition process.In liquid, form nano particle in the liquid by depositing to.
For the present invention is described, describe the method for preparation and sign different materials below in detail.Use dropper to prepare sample less than 1 millimeter with surface, about 1.5 square inches (3.8 centimetres) degree of depth of covering of the wetting clear float glass substrate of ionic liquid (IL).Use scraper to help liquid to sprawl from the teeth outwards.Contain the square that ion liquid glass substrate is 3 inches (7.6cm).Substrate places on the support plate then, is placed in the inlet cabin (lock) of Airco Temescal ILS 1600 vacuum coater, vacuumizes before entering the sediment chamber, makes base pressure less than 10 -6Torr.Between 1-7 micron Hg, pass through all coatings of DC magnetron sputtering deposition.Substrate moves under sputtering target with the speed (3m/min) of 120 inch per minute clocks.Pressure does not change after containing ion liquid sample to enter the sediment chamber or in deposition process.Use Tencor P1 contact pin type profilometer to measure coat-thickness, unless other explanation is arranged.
Embodiment 1
This embodiment illustrates the formation of copper nano particles.With 1.5kW firm power, 508 volts of voltage, 2.95 ampere electric currents, in argon gas atmosphere under 4 microns Hg pressure by copper target deposited copper.Substrate passes through target 20 times.After deposition, from the sediment chamber, take out sample.As desired, around ionic liquid (above-mentioned [BMIM] PF 6) glass surface area cover copper film.Yet ionic liquid does not change, and except transmission manifests color russet, develops into viridant composition after about 4 minutes.If the ionic liquid that contains copper was placed 4 minutes in coating machine under vacuum at least, take out then, ionic liquid is a sorrel color and do not present green so.Yet color changes after about 4 minutes, as previously described.If covering sample with sheet glass when coating machine takes out, solution keeps sorrel and does not develop into green.This shows some copper particles in ionic liquid because oxygen and water vapor in the atmosphere can form copper oxide or copper oxyhydroxide, and/or some particles are reunited.
When removing when collecting the catch tray from glass baseplate surface by clean the ionic liquid will contain copper with acetone, once had ion liquid position and do not have coating, have the obvious border that forms by copper film.This shows that sedimentary copper is retained in the ionic liquid on ionic liquid, does not outgas, splashes or react at the Liquid Thin membrane boundary before deposition or in the deposition process.Use the boundary survey film thickness to be 353nm.Measure the density calculation that obtains by XRF, equal the copper of about 344 μ g/ square centimeters from the copper film of sputter.
Use LEO 1530SEM and Noran Vantage EDS/EDX respectively, analyze the copper particle that present method is formed by FESEM (field-emission scanning electron microscope) and EDX (energy dispersion X ray) and analyze.The advantage of using this analysis is to carry out visual observation to particle, and can use FESEM analysing particulates size, uses EDX to carry out element and identifies.From the ionic liquid volume, take out the particle of reuniting,, reduce the ionic liquid scale of construction and increased particle signal intensity because influence each other from ion liquid background signal and particle signal.The particle that from ionic liquid, only takes out agglomerating particles or reunite owing to the taking-up process.In dish, use acetone to dilute the ionic liquid several times that contain copper in addition, remove acetone and ionic liquid with filter paper, further dilute, pour out liquid then, thereby take out particle with 50% Virahol-deionized water mixture in each dilution back.Process makes the copper particle of reuniting be retained in the ion liquid residuum of dilution, and its part is transferred to then
Figure A200780005200D00111
Carrying out FESEM on the board adhesive tape analyzes.The particle suspension of Tuan Juing is not in ionic liquid.The particle of not reuniting by the spectrophotometry alleged occurrence.
Spectrophotometry and analysis are to exist absorption peak to determine to exist another measuring technology of nano particle by observing at specific wavelength.Especially, use metal surface plasma resonance (SPR) (it is particulate material and size and the function that contains granule medium) to determine the existence of metal nanoparticle in ionic liquid in solution at characteristic wavelength.The advantage of this technology is that particle remains in the solution and is in the state of not reuniting.Deduct for a short time of ion liquid background signal, if perhaps the ionic liquid signal is compared with sample signal and can be ignored, the ionic liquid signal can be ignored so.As mentioned above, sample also can seal with isolated from atmosphere, and measures.
Use the spectrophotometry analysis to contain the ionic liquid sample (i.e. ionic liquid before dilution, as in embodiment 1, discussing) of copper to determine existing of copper nano particles.The sample demonstration of test does not comprise any visual agglomerating particles.Two types absorption spectrum of measure sample: after taking out, be exposed to atmospheric sample (be called is " exposure "), and taking out the sample (be called is " sealing ") that the back covers, seals immediately with the transparent float glass plate from coating machine from coating machine.Use Perkin-Elmer Lambda 2 UV/VIS/NIR spectrophotometers to measure the sample that exposes at 300-1100nm.For the transparence in UV spectrum district, use quartz cell (curvets) (Fisher Far UV rectangle 1mm) to hold the sample of exposure.Measure the sample of two exposures: contain the ionic liquid of copper and contain copper and with the sample (be called is " dilution ") of the additional ions liquid diluting of same type.
The TCS spectrophotometer that use can obtain from BYK Gardner USA is at 400-700nm measurements sealed sample.Use the TCS spectrophotometer, this is that transmissivity is from descend fast less than 350nm (for 2.3mm thickness, 350nm83% is to 300nm 3.5%) because float glass is penetrable hardly at ultraviolet region.Yet, have characteristic absorption wavelength in the visible range.
Fig. 1 shows 3 kinds of ion liquid specific absorptioies that contain copper.Sealed sample demonstrates absorption peak at about 580nm.This absorbs owing to the surface plasma resonance (SPR) that overall dimension is not more than the copper nano particles of 100nm.Believe that for Cu sample that expose and dilution the absorption that sharply begins at the 500nm place shows and has copper oxide and copper hydroxide nano particle.
Fig. 2 and 3 is presented at the FESEM of the agglomerated copper particulate samples in the residual ion liquid on the Scotch board adhesive tape.Owing to be difficult to from ionic liquid, take out the particle that therefore copper be limited to this sampling fully, demonstrate particle overall dimension and be not more than 100nm.The upper limit of their expression particle sizes.EDX among Fig. 4 analyzes and shows from copper in the ionic liquid and background phosphorous (P).
Embodiment 2
This embodiment illustrates the formation of silver nano-grain.The similar mode depositing silver of method with the deposited copper described with embodiment 1.With 3.0kW firm power, 599 volts of voltage, 5.0 amperes in argon gas atmosphere at 4 microns Hg pressure deposit silver.Substrate passes through 10 times under silver-colored target.Remove from glass substrate and collect the catch tray by in acetone, cleaning the ionic liquid to contain silver.At film with uncoated to contain ion liquid interregional boundary survey silver film thickness be 463nm.Measure the density calculation that obtains by XRF, equal the silver of about 470 μ g/ square centimeters from the silverskin of sputter.In dish, dilute the ionic liquid several times that contain silver in addition, remove acetone and ionic liquid with filter paper in each dilution back with acetone, thus the taking-up particle.Make acetone evaporated up to the surplus film that the silver nano-grain of reunion is arranged then.Then film transfer is carried out FESEM and EDX analysis to Scotch board adhesive tape.The particle of Tuan Juing is not retained in the suspension, obtains the particle of not reuniting when removing acetone.The particle of not reuniting by the spectrophotometry alleged occurrence with the same way as that is used for copper.The FESEM pictorial display by size less than the 10nm silver of the granuloplastic reunion of about 100nm (referring to Fig. 5 and 6) at the most.Analyze the particle of alleged occurrence elemental silver by EDX.Use ThermoElectron ThetaProbe (Thermo Electron Corporation, whether West Sussex England) further analyzes to detect silver the taking-up on Scotch board adhesive tape silver sample by XPS (x-ray photoelectron spectroscopy) and reacts with ionic liquid.As desired, the surface of sample demonstrates carbon, oxygen and fluorine contaminant.After use is removed surface contaminant with the argon ion bombardment (sputter) of 2kV acceleration voltage, only leave silver.This is by existing silver metal 3d 5/2Photoelectron is confirmed.Fig. 7 shows the XPS intensity that is fixed on the silver on the adhesive tape.Sputter after 60 seconds F1s blackout and Ag3d signal strengthen, show only to have silver-colored particle, do not react with ionic liquid.0 signal is owing to adhesive tape.
The ion liquid spectrophotometry that also contains silver with the describing mode of described measurement copper.Transfer to quartz cell and on Lambda2, measure will being exposed to the atmospheric ionic liquid that contains silver after the deposition.The nano particle of some reunions separates from solution, and specimen does not comprise any visual agglomerating particles.Fig. 8 in spectrum show sample at the strong absorption peak of the silver at about 410nm place.This is because the surface plasma resonance (SPR) of silver nano-grain absorbs.This measurement shows the reaction that does not exist with ionic liquid or atmosphere (moisture content or oxygen) with XPS measuring.
The result of these analyses shows by the generation of depositing silver in ionic liquid silver nano-grain.Particle has at the most 100nm, for example 50nm or the overall dimension of 10nm at the most at the most.
In addition, these results show that for copper and silver the nano particle of maximum enters in the effects of ion liquid and is retained in the effects of ion liquid, and any this peaked particle that surpasses will be reunited.
Embodiment 3
This embodiment illustrates that the tungsten oxide nanometer particulate forms.With aforesaid method deposition Tungsten oxide 99.999.At 50% O 2With in the reactive gas atmosphere of 50% Ar by at 4 microns Hg pressure current downflow deposition tungsten targets.Operate target with 3.0kW firm power, 486 volts of voltages, 6.24 ampere electric currents.Substrate passes through 10 times under target.Remove from glass substrate and collect the catch tray by in acetone, cleaning the ionic liquid to contain Tungsten oxide 99.999.Tungsten oxide 99.999 117nm thick (measuring in the above described manner).The ionic liquid that contains Tungsten oxide 99.999 when viewed in transmittance has yellow appearance.Believe that this colour generation is owing to exist Tungsten oxide 99.999 or plasma body and ionic liquid to react in ionic liquid.At first in dish, contain the ionic liquid of Tungsten oxide 99.999 and remove acetone and ionic liquid, thereby take out particle with filter paper with acetone diluted.Yet find that do not have visual reunion, any ion liquid effort of removing acetone diluted causes absorbing liquid and WO 3Therefore, make acetone evaporated.Then remaining ionic liquid solution is mixed with 50% Virahol-50% deionized water mixture, the result forms the little drop (diameter is less than 1mm) of the solution that contains Tungsten oxide 99.999.Droplet transfer to silicon substrate, is handled in SPIPlasma-Prep II plasma asher to remove some ionic liquids, used FESEM, EDX and XPS to analyze.XPS confirms that drop contains WO 3XPS figure (referring to Fig. 9) shows for the sample on the silicon substrate, in the tungsten oxide peak of 35.8eV at 4F 7/2And 4F 5/2Peak-to-peak have a 2.2eV division.(referring to the material database of http://srdata.nist.gov/xps/index.htm XPS peak position).FESEM image (referring to Figure 10 and 11) shows the individual particle of Tungsten oxide 99.999.The pictorial display particle also demonstrates the overall dimension that is not more than about 120nm, for example is not more than 50nm or is not more than 10nm.Particle also demonstrates the sphere of sharp outline.EDX (referring to Figure 12) alleged occurrence elemental tungsten.
Embodiment 4
This embodiment illustrates increases viscosity of il to change the performance of deposition material.
Find that the decision of ion liquid viscosity is when whether forming nano particle or film during deposition material by PVD on ionic liquid.In order to be explained, increase ion liquid viscosity by dissolve polymer in ionic liquid, magnetron sputtering deposition differing materials on solution.
By at 0.14 gram/ml[BMIM] PF 6Add polyvinylpyrrolidone (PVP) powder (type NP-K30 is by the commercially available acquisition of GAF company) in the enriched material and make viscous solution.Transparent to obtain at 90 ℃ of heating this solution 35 minutes then, the unusual sticking solution of heavy-gravity obviously do not flow when cool to room temperature (21 ℃).3 " * 3 " (solution is sprawled the circle that forms diameter about 1.5 inches (3.8cm) on the thick sheet glass of 7.6cm * 7.6cm), 2.3mm, be fixed to 12 " * 12 " (36.5cm * 36.5cm) support plate goes forward to make surface " smoothly " several minutes, and places vacuum chamber.
By two samples of the preparation of magnetron sputtering deposition on the PVP-ionic liquid solution.Prepare first sample with the similar mode depositing silver of method for silver and copper with previous description.1kW firm power, 476 volts of voltage, 2.1 amperes in argon gas atmosphere at 4 microns Hg pressure deposit silver.Substrate passes through 30 times under silver-colored target.Silver layer on glass substrate estimates that 300nm is thick.Deposit second sample to form the low emissivity coatings that multilayer is used for general type on glass.Coating comprises following layer by the magnetron sputtering sequential aggradation: Zn 2SnO 4/ Zn-10 weight %Sn/Ag/Ti/Zn 2SnO 4/ Zn-10 weight %Sn/Ag/Ti/Zn 2SnO 4(being called " Ag dielectric lamination ") at this.Known this types of coatings is as " high T/ hangs down E " (high-transmission rate/low-launch-rate) coating, at United States Patent (USP) 4,898, is described in 789 and 4,898,790.After deposition, from the sediment chamber, take out coating and carry out visual detection.Compare with the pattern of sedimentary nano particle sample in pure ionic liquid, on the PVP-ionic liquid solution, coating occurs.The common pattern of coating coating common and on the adjacent glass surface is identical on the solution.Because the inhomogeneous character of following fluidic, silvered film has light emblem wrinkle pattern.Laminated coating has some crackles, may be because the flowing and adhere on the coating of solution.The square that covers accompany accompany for formula support store October in the ware after, laminated coating still has general pattern identical when depositing originally.Because the edge exposes, the coating around the crackle can slight degradation.For this types of coatings, this can reckon with.In phase after the contemporaneously, a part of silver coating has light and translates as a part of silver coating on the contiguous glass surface.And other parts tarnish.Spectrum among Figure 13 shows the PVP-ionic liquid solution and is coated with the percent transmittance of glass substrate between the 300-2500nm after October of Ag-dielectric lamination.Compare with glass substrate, transmissivity is in the slight reduction of visible region (400-780nm), and the slight increase in infrared solar radiation light district (800-2500nm).This is owing to have crackle in the coating on the PVP-ionic liquid solution.Consider coating not protected (when commerce was used, these coatings sealed) in unitary dry inert gas and on the PVP-ionic liquid solution October, show [BMIM] PF 6Can ignore corrosive nature based on the coating of silver.
Although do not measure the viscosity of solution, be that particle or film have obvious influence for decision form of sedimentary material on solution can understand viscosity.Pure [BMIM] PF 6The published value of viscosity is 312 centipoises (cP).In nonrestrictive embodiment, can be not more than 1500cP for implementing the suitable viscosity of il of the present invention in room temperature (23 ℃), for example be not more than 1110cP, for example 66-1110cP.When soltion viscosity increased, particles no longer entered solution, but formed film on solution, and promptly flow (flux) of deposition material seems to show to such an extent that more similarly be solid surface rather than fluid surface.In solution, form the particulate range of viscosities and will influence for example size and shape of particulate performance.This can and deposit acquisition by solute concentration in the reduction ionic liquid on solution.Can use any material that has in the ion liquid solution and be suitable for PVD that enters.
For the foregoing description, before deposition, add polymkeric substance and form with control film or particle.The specified property of solution or particle or film can or add different polymkeric substance or the ionic liquids of measuring before deposition so after the deposition or before deposition and after deposition if desired.For example, has particular particle size in the viscosity that is different from the solution final viscosity if desired, solution to the preparation particular particle size applies so, adds additional polymkeric substance or ionic liquid to obtain the required viscosity of final polymkeric substance-ionic liquid solution after deposition.Polymkeric substance can be identical or different polymkeric substance.Also can adjust ionic liquid, can add the ionic liquid combination to obtain required solution with polymkeric substance or combination of polymers.In all cases, polymkeric substance can be substituted by monomer, and monomer can carry out polymerization after deposition.In interchangeable application, can remove polymkeric substance and leave ionic liquid or wash ionic liquid and polymkeric substance in the solution, be used for the self-supported membrane (free standing film) of subsequent disposal precedent such as pigment flakes with preparation.In Another Application, have on solution in coating deposited or the solution particulate layer can with other material organic or inorganic layer or carry out lamination for polymkeric substance or glass coating more specifically for example.
Ion liquid viscosity can influence particulate distribution of sizes in the ionic liquid.If viscosity is enough high, can on ionic liquid, deposit one or more layers film.Can dissolve in a usual manner subsequently or deionizing liquid to leave film, it can be used for pigment or introducing has or do not have the medium of pigment.For the various ionic liquids that have discrete particles therein, ionic liquid can be used as the reactant of further carrier of handling of particulate or the further treatment step of conduct.
Embodiment 5
This embodiment explanation prepares the method for nanoparticle catalyst in ionic liquid.
Can protective agent for example in the presence of tensio-active agent, polymkeric substance or the organic ligand (to avoid particle agglomeration) by the reduction or the oxidation of metallic compound, chemistry obtains to have the stable transition metal nanoparticles of controlled size and composition.Reported chemosynthesis and the use of transition-metal catalyst in ionic liquid recently.Ionic liquid makes it possible to prepare transition metal nanoparticles and makes it stable, can carry out the catalyzer recycling easily and carry out product separation.The advantage of the nano particle of use in ionic liquid is can repeatedly reuse catalyzer in catalyzed reaction and do not have significant loss in catalytic activity.Ir and Ru have been prepared with the preparation catalyst system.
Physical vapor deposition provides interchangeable method in ionic liquid, it only needs a step process, there is not chemical by-product, reusing and need not easily before deposition or preparing nano particle in the stable of interpolation reagent with the prevention particle agglomeration after the deposition, although after deposition, can add reagent.
In order to describe, by at [BMIM] PF 6[BMIM] BF 4Solution on carry out the Ir magnetron sputtering deposition and prepare sample.To prepare sample by Ir target deposition iridium with the previously described similar mode of method for silver and copper.3kW firm power, 590 volts of voltages of electricity, 5.08 amperes in 100% argon gas atmosphere at 4 microns Hg pressure deposit iridium.Substrate passes through 15 times under the iridium target.Taking out the back viewed in transmittance from the sediment chamber, the ionic liquid that contains Ir has brownish outward appearance.Use scanning electronic microscope (SEM) to measure cross section, iridium layer 120nm on glass is thick.
[BMIM] BF that contains the Ir nano particle 4Transfer to and carry out the FESEM analysis on the carbon substrate.On carbon substrate, place a small amount of (about 5) and carry out the FESEM analysis.Use small amount of deionized water dilution ionic liquid solution, cause the Ir nanoparticle agglomerates.Make the water drying, cause the dilution of nanoparticle agglomerates and drying process to repeat several times.The FESEM that shows the Ir nano particle in the drawings.EDX alleged occurrence Ir among Figure 15.
Embodiment 6
Except that material discussed above, at ionic liquid ([BMIM] PF 6) last magnetron sputtering deposition Ti, TiO 2, Zn 2SnO 4, Si-10 weight %Al oxide compound, zinc-10 weight % stannic oxide and Ag oxide compound.Also deposit multilayer coating on ionic liquid.Coating comprises the layer below by the magnetron sputtering sequential aggradation: Zn 2SnO 4/ Zn-10 weight %Sn/Ag/Ti/Zn 2SnO 4/ Zn-10 weight %Sn/Ag/Ti/Zn 2SnO 4Other by two fluoroform sulfimide salt ([the EMIM] (CF of 1-ethyl-3-Methylimidazole 3SO 2) 2N), 1-butyl-3-methyl imidazolium tetrafluoroborate ([BMIM] BF 4), 1-hexyl-3-methyl imidazolium tetrafluoroborate ([HMIM] BF 4) on the ionic liquid that constitutes in mode described here by magnetron sputtering deposition copper and silver.As shown in figure 16, as described here, these contain spectrophotometry and [BMIM] PF of the liquid of silver 6Mensuration show that demonstrate strong absorption peak at about 410nm, this is because the surface plasma resonance (SPR) of silver nano-grain absorption in the ionic liquid solution.As can be known from Fig. 14, particle demonstrates little more many than 200nm, for example is not more than 50nm, for example is not more than 10nm agglomeration nano particulate structure.
Believe, anyly can carry out sedimentary material by physical vapor deposition (PVD) and the time can cause the stabilized nano particle solution when deposition in ionic liquid.For example, can pass through PVD for example magnetron sputtering deposition or carbon arc deposit carbon on ionic liquid, with preparation carbon nano-particle, for example carbon nanotube.By magnetron sputtering deposition at [BMIM] PF 6Middle deposition indium tin oxide (ITO) nano particle.The ITO nano particle can be used for preparing the conductive particle that does not absorb at visible region.By magnetron sputtering deposition at [BMIM] PF 6Middle deposition of titanium oxide nano particle.Titania nanoparticles can be used for preparing nanocatalyst.
Embodiment 7
Example as contain the nano particle of polymkeric substance from the il electrolyte electrochemical deposition that contains nano particle by method preparation described here is containing [BMIM] PF of silver nano-grain 6In the electrolyte solution from EDOT (3,4-vinyl dioxy thiophene) monomer solution by electrochemical deposition growth conductive polymers PEDOT (poly-3,4-vinyl dioxy thiophene).Directly on the TEM grid, prepare film.The TEM measurement is presented at has the Ag nano particle in the conductive polymers matrix.
This method allows in electrodeposition process by using the conducting polymer thin film with various doped level of voltage formation from neutral (insulating) to mix fully (conduction) that is fit to.Except that electric look demonstration and organic light-emitting devices application, this hybrid material also is interested in the application of thermoelectric and optoelectronic equipment.
Method is not restricted to above-mentioned materials, but can be suitable for the monomer of any electrochemical polymerization and the nano particle of any kind.
Ion liquid other application that contains nano particle comprises sterilant, battery, pigment, lubricant, makeup.Substrate is film, strainer, fabric and the available ionic liquid dipping that contains nano particle of nanoporous pottery for example, depends on application, type of substrate or substrate pre-treatment, and substrate deionizing liquid capable of washing leaves the nano particle of distribution in the substrate hole.But substrate flexible or inflexible or transparent or opaque.A kind of particularly suitable film is by PPGIndustries, and Inc makes
Figure A200780005200D00181
Film.
Effect to the particle performance
Move because be used for the substrate of these experiments, in ionic liquid, collect the particle of broad distribution of sizes, shown in the FESEM image.For example be applied to the power of target or substrate speed (being included in the deposition on the fixing base) and substrate-range by deposition parameter and determine particularly particulate size and dimension of sedimentary material forms from, gas and vacuum chamber pressure.Angle between source and substrate (when substrate moves, not considering) remarkably influenced particulate size and dimension.Single-size distributes to select will to provide more with the straight fixing base in source, shielding low angle incident particle.Perhaps, on substrate, will cause particle size distribution from source collecting granules (as distance and/or angle function) from the source.In addition, shown that particle volume is directly proportional with pressure, thereby shown importance with liquid compatible with particle with vacuum system.Ionic liquid character for example viscosity, temperature, thickness, chemical constitution will influence particulate character.Particularly, sputter is the atomic deposition process of accurately controlling dimension.Can change or hybrid alloys target or cosputtering target and gas composition with deposition material, for example from argon-oxygen-nitrogen gas mixture deposition oxynitride.Yet, other method of may command for example heat or electron beam evaporation or cathodic arc deposition with the particle of the wide size range of high deposition rate preparation from nano particle to the hundreds of micron.By above-mentioned discussion as can be known, ionic liquid need not to comprise that tensio-active agent is to stop particle agglomeration.
Contain the reaction of particulate liquid
The ionic liquid that contains nano particle can combine with other material to give the mixture supplementary features of gained.Usually, described in the prior art and used ion liquid several types polymerization, comprised homopolymerization, statistical copolymerization, block copolymerization and polymkeric substance-ionic liquid composites.Can use the ionic liquid that contains nano particle that makes by the inventive method to carry out these types of polymerization to avoid multistep treatment step as described in the prior art.
For example, the ionic liquid that contains copper, silver or silver suboxide of exposure combines with cyanoacrylate (Permabond910FS binding agent) to form soft solid materials.As another embodiment, the ionic liquid that contains silver combines with urethane oligomers/methacrylate monomer admixture (Kemkert KaoOptical binding agent 300), solidifies under 320-380nm UV.Mixture is clipped between two transparent float glass, and UV solidifies with preparation glass/polymer (being made of curing mixture)/glass stack then.In another embodiment, the Elvacite acrylic resin is dissolved among the DowanolPM (glycol ethers PM), adds [BMIM] BF that contains nano particle in solution 4[BMIM] PF 6[BMIM] BF that contains the Ir nano particle 4Form gel, and be heated to 132 ℃ XXX minute to form soft solid materials.Clean soft solid materials to remove resistates at acetone.Soft solid materials keeps initially containing the brown of ionic liquid solution, shows to have the Ir nano particle.In identical solution, add [BMIM] BF that contains ZnO that makes by method described here 6With [BMIM] BF that contains the ITO nano particle 6, to form soft solid materials, show that nano particle can introduce in the plastic substrate 132 ℃ of heating 12 hours.
By above-mentioned discussion as can be known, can will be dispersed with particle therein or form film on it or ionic liquid that the both has further is treated to various products.For example, can add additive or reactant to form solid, for example introduce the plastics of particle or film to ionic liquid.Or ionic liquid can be used for the solvent of further processing or reaction.
In liquid, carry out sedimentary device
In ionic liquid, carry out sedimentary device and comprise container as the ionic liquid holder.Container is placed on the position that when by the processes of physical vapor deposition deposition material, will catch at that time.Container can contain ionic liquid is transported to container and/or will contains import and the outlet that the particulate ionic liquid takes out from container.Container can contain cooling or heat ion liquid any conventional device.The gangway can for example be extracted in vacuum or the inert atmosphere at controlled environment.Extraction can transmit liquid and further handle.
Can use the alternate manner that contains liquid described in the prior with ionic liquid.These comprise conventional VEROS technology or its improvement, or conventional VERL technology or its improvement, for example respectively as S.Yatsuya, Y.Tsukasaki, K.Mihama and R.Uyeda, J.Cryst.Growth:43,490 (1978) and I.Nakatani, T.Furubayashi, J.Magn.Magn.Mater.122 (1993) 10 describes.
It will be readily appreciated by those skilled in the art that under the condition that does not break away from disclosed thought in the above-mentioned specification sheets and can change the present invention.Think that this change comprises within the scope of the invention.Therefore, only be illustrative in specifically described special embodiment above, and do not limit the scope of the invention, provide complete scope of the present invention by accessory claim and its any and whole equivalent way.

Claims (28)

1. prepare the particulate method, comprising:
In the sediment chamber, introduce ionic liquid; And
Introduce one or more materials so that particle to be provided by physical vapor deposition to ionic liquid in ionic liquid.
2. the method for claim 1 also comprises and is found time in the sediment chamber.
3. the method for claim 2, the vacuum that is not more than 10 microns Hg to provide of wherein being found time in the sediment chamber.
4. the method for claim 2, the vacuum that is not more than 7 microns Hg to provide of wherein being found time in the sediment chamber.
5. the process of claim 1 wherein that described particle has the diameter that is not more than 500nm.
6. the process of claim 1 wherein that described particle has the diameter that is not more than 200nm.
7. the process of claim 1 wherein that described particle has the diameter of 1-200nm.
8. the process of claim 1 wherein that described ionic liquid comprises at least a following positively charged ion that is selected from: single, two and trisubstituted imidazoles, the pyridine of replacement, the tetramethyleneimine of replacement, Si Wan Ji Phosphonium, tetra-allkylammonium, guanidine, isourea, thiocarbamide.
9. the process of claim 1 wherein that described ionic liquid comprises at least a following negatively charged ion that is selected from: chlorion, bromide anion, iodide ion, tetrafluoroborate, hexafluoro-phosphate radical, two (trifluoromethyl sulphonyl) imines roots, three (pentafluoroethyl group) trifluoro phosphate radicals (FAPs), trifluoromethanesulfonic acid root, trifluoracetic acid root, methylsulfate, octyl group sulfate radical, thiocyanate ion, organic boronic root, and tosic acid root.
10. the process of claim 1 wherein that described ionic liquid is selected from 1-butyl-3-Methylimidazole hexafluorophosphate ([BMIM] PF 6), 1-hexyl-3-methyl imidazolium tetrafluoroborate ([HMIM] BF 4), 1-butyl-3-methyl imidazolium tetrafluoroborate ([BMIM] BF 4) and two fluoroform sulfimide salt ([the EMIM] (CF of 1-ethyl-3-Methylimidazole 3SO 2) 2N).
11. the process of claim 1 wherein that described ionic liquid has the viscosity that is not more than 1110cP 23 ℃ temperature.
12. the process of claim 1 wherein and carry out deposition step by magnetron sputtering or electron beam evaporation.
13. the method for claim 12 is carried out sputter in reaction atmosphere.
14. the method for claim 12 is wherein carried out sputter in the atmosphere of vacuum.
15. the method for claim 12 is wherein carried out sputter in inert atmosphere.
16. the process of claim 1 wherein that described ionic liquid comprises two or more ion liquid mixtures.
17. the method for claim 1 comprises and regulates ion liquid viscosity.
18. the method for claim 17 is wherein carried out regulating step by add one or more polymkeric substance or monomer to ionic liquid.
19. the method for claim 1 comprises to ionic liquid and adds one or more monomers or polymkeric substance.
20. the method for claim 19 comprises that monomer or polymkeric substance are reacted with formation contains the particulate polymeric material.
21. prepare the method for nano particle, comprising:
In the sediment chamber, introduce ionic liquid;
Find time the sediment chamber to form the vacuum that is not more than 7 microns Hg in the sediment chamber; And
One or more negative electrodes of sputter are to introduce one or more materials to ionic liquid so that nano particle is provided in ionic liquid in the sediment chamber.
22. apply ion liquid method, comprising:
In the sediment chamber, introduce ionic liquid;
Find time the sediment chamber to form the vacuum that is not more than 7 microns Hg in the sediment chamber; And
One or more negative electrodes of sputter are filmed so that form on ionic liquid to introduce one or more materials to ionic liquid in the sediment chamber.
23. composition comprises:
Ionic liquid; And
By physical vapor deposition sedimentary particle in ionic liquid.
24. the composition of claim 23, wherein particle has the size that is not more than 500nm.
25. the composition of claim 23 comprises one or more monomers or polymkeric substance.
Comprise grains of composition 26. the method by claim 1 makes.
27. the film that the method by claim 21 makes.
28. preparation particulate device comprises:
The sediment chamber; And
Ion liquid container, design containers be with capture material when depositing by processes of physical vapor deposition in the sediment chamber, and container comprises ionic liquid is transported to container and/or will contains import and the outlet that the particulate ionic liquid takes out from container.
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